Thiobis(oxazolines)

ABSTRACT

Lactone oxazoline reaction products of hydrocarbon substituted lactone carboxylic acids, for example, polybutyl lactone carboxylic acid, with 2,2-disubstituted-2-amino-1-alkanols, such as tris-(hydroxymethyl)aminomethane (THAM), and their derivatives are useful additives in oleaginous compositions, such as sludge dispersants for lubricating oil, or anti-rust agents for gasoline.

This is a division of application Ser. No. 726,206, filed Sept. 24,1976, now U.S. Pat. No. 4,062,786, issued Apr. 13, 1977.

BACKGROUND OF THE INVENTION AND PRIOR ART

The present invention concerns hydrocarbon soluble alkyl lactoneoxazolines, their method of preparation, the utility of said lactoneoxazolines in hydrocarbon fuel and lubricating systems as highly stableanti-rust agents and/or sludge dispersants.

During the past decade, ashless sludge dispersants have becomeincreasingly important, primarily in improving the performance oflubricants and gasoline in keeping the engine clean of deposits, andpermitting extended crankcase oil drain periods. Most commercial ashlessdispersants fall into several general categories. In one category, anamine or polyamine is attached to a long chain hydrocarbon polymer,usually polyisobutylene, obtained by the reaction of halogenated olefinpolymer with polyamine as in U.S. Pat. Nos. 3,275,554; 3,565,592;3,565,804. In another category, a polyamine is linked to thepolyisobutylene through an acid group, such as a long chainmonocarboxylic acid, e.g., see U.S. Pat. No. 3,444,170 or a long chaindicarboxylic acid such as polyisobutenylsuccinic anhydride, by formingamide or imide linkages, such as described in U.S. Pat. Nos. 3,172,892;3,219,666; etc. In still another category the amines and polyamines arelinked to the polyalkyl chain through a dicarboxylic acid lactone suchas described in U.S. Pat. Nos. 3,200,075; 3,261,782; 3,897,350;3,936,472, etc.

U.S. Pat. No. 3,261,782 teaches that alkylbutyrolactone--α acetic acidsthemselves are useful rust inhibitors in lubricating oil compositionswhich acids are derived from long chain dicarboxylic acids.

Reaction products of hydrocarbon substituted succinic anhydride, e.g.,the aforesaid polyisobutenylsuccinic anhydride, with compoundscontaining both an amine group and a hydroxy group have been suggestedor investigated in the prior art. For example, U.S. Pat. No. 3,272,746teaches the reaction of ethanolamine and diethanolamine, as well asvarious hydroxyalkyl substituted alkylene amines, such asN-(2-hydroxyethyl) ethylene diamine, N,N'-bis(2-hydroxyethyl) ethylenediamine, with alkenyl succinic anhydride to obtain ashless dispersantsfor lube oil. A hydroxy amine, such as diethanolamine, is reacted with along chain alkenylsuccinic anhydride in U.S. Pat. No. 3,324,033 to forma mixture of esters and amides, wherein some of the diethanolaminereacts through a hydroxy group to give an ester linkage, while anotherportion of the diethanolamine forms an amide linkage.

United Kingdom Specification No. 809,001 teaches corrosion inhibitorscomprising a multiple salt complex derived from the reaction product ofhydrocarbyl substituted dicarboxylic acids and hydroxy amines (including2-amino-2-methyl-1,3-propanediol [AMPD]) andtris-hydroxymethylaminomethane (THAM) further complexed with mono- andpolycarboxylic acids (see Examples 17-19).

U.S. Pat. No. 3,576,743 teaches reacting polyisobutenylsuccinicanhydride with a polyol, such as pentaerythritol, followed by reactionwith THAM, (see Example 1). U.S. Pat. No. 3,632,511 teaches reactingpolyisobutenylsuccinic anhydride with both a polyamine and a polyhydricalcohol including THAM. U.S. Pat. No. 3,697,428 (Example 11) teachesreacting polyisobutenylsuccinic anhydride with a mixture ofpentaerythritol and THAM. United Kingdom Pat. No. 984,409 teachesashless, amide/imide/ester type lubricant additives prepared by reactingan alkenyl succinic anhydride, said alkenyl group having 30 to 700carbon atoms, with a hydroxy amine including THAM.

DOS 2512201 teaches reacting long chain hydrocarbon substituted succinicanhydride with 2,2'-disubstituted-2-amino-1-alkanol to produce mono- andbis-oxazoline products (see also DOS No. 2534921/2 for similar reactionproducts which can also be modified by reaction with phosphorus, boronor oxygen compounds).

The earlier referenced category of dicarboxylic acid lactone typeproducts have also been provided with anti-rust and/or dispersantproperties by reaction with hydroxy amines such as ethanolamine anddiethanolamine (see U.S. Pat. Nos. 3,248,187 and 3,620,977).

SUMMARY OF THE INVENTION

As noted above, the prior art teaches oil-soluble additives formed fromhydrocarbyl substituted dicarboxylic acid material which has beenconverted into a lactone and reacted with various amino or hydroxycompounds either through an amide, imide or ester linkage, and thatthese additives are stated to be useful for various functions, such asanti-rust agents, detergents, or dispersants for oleaginous compositionsincluding lube oil, gasoline, turbine oils and oils for drillingapplications.

It has now been discovered that long chain hydrocarbon structures whichfeature vicinal lactone and oxazoline ring systems can be so constructedusing novel synthetic methods whereby a highly stable additive ofenhanced dispersancy, enhanced viscosity properties, and/or anti-rustproperties is obtained. Moreover, further functionalization of this dualheterocyclic system via our new processes with vicinal hydroxyl, thiyland sulfo groups can engender other desirable properties, such asanti-oxidation and anti-corrosion activity. This novel class ofadditives can be represented in part by the formula: ##STR1## wherein Ris selected from the group consisting of hydrogen and alkyl radicalscontaining from 1 to 400 or more carbons, X is selected from the groupconsisting of an alkyl or hydroxy alkyl group and at least one of the Xsubstituents and preferably both of the X substituents being a hydroxyalkyl group of the structure --(CH₂)_(n) OH where n is 1 to 3 and Y isselected from the group consisting of hydrogen, hydroxyl, sulfo,alkylthio (TS--), alkyldithio (TSS--), and a sulfur bridge, e.g., --S--and --S--S--, joining two lactone oxazoline units together as depictedbelow wherein z is a number ranging from 1 to 4 and T is definedhereafter as containing 1 to 50, preferably 2 to 20 carbons. ##STR2##Preferred herein is polyisobutyl lactone oxazoline of number averagemolecular weight ranging from about 400 to 100,000 prepared by thereaction of equimolar proportions of polyisobutyl lactone carboxylicacid with tris-[hydroxymethyl] aminomethane at a temperature from about100°-240° C. preferably 150°-180° C. until two moles of H₂ O per mole ofreactant is removed from the reaction.

The novel compounds described above as effective detergents inlubricating oil compositions are also useful as detergents in fuelcompositions, such as burner fuel compositions, and motor fuelcompositions, for example, in gasolines and in diesel fuels. Thus, it iswithin the scope of this invention to dissolve a small but at least aneffective amount of said compounds of the invention in a majorproportion of an oleaginous material to provide useful oleaginouscompositions.

These hydrocarbon soluble compounds have at least 8 carbons in thesubstantially saturated aliphatic hydrocarbyl group and a carboxylicacid group of the dicarboxylic acid material converted into a lactonering and another carboxylic acid group converted into an oxazoline ringas a result of the reaction of at least equimolar amounts of saidhydrocarbon substituted dicarboxylic acid lactone material and a2,2-disubstituted-2-amino-1-alkanol having 1 to 3 hydroxy groups andcontaining a total of 4 to 8 carbons.

These novel alkyl lactone oxazolines of the present invention can beprepared as noted by heating together alkyl lactone acids, esters oramides with a 2,2-disubstituted-2-amino-1-alcohol, such astris-(hydroxylmethyl) aminomethane, as expressed in the followingequation: ##STR3## wherein R is as previously defined and Q is assubsequently defined.

ALKYL LACTONE REACTANTS

The preparation of the requisite reactants involves a lactonization ofan alkenyl succinic acid analog obtained via the Ene reaction of anolefin with an alpha-beta unsaturated C₄ to C₁₀ dicarboxylic acid, oranhydrides or esters thereof, such as fumaric acid, itaconic acid,maleic acid, maleic anhydride, dimethyl fumarate, etc. The dicarboxylicacid material can be illustrated by an alkenyl substituted anhydridewhich may contain a single alkenyl radical or a mixture of alkenylradicals variously bonded to the cyclic succinic anhydride group, and isunderstood to comprise such structures as: ##STR4## wherein R may behydrogen or hydrocarbyl or substituted hydrocarbyl each having from 1 toabout 400 and more carbons, and preferably from 1 to about 200 carbonatoms. The anhydrides can be obtained by well-known methods, such as thereaction between an olefin and maleic anhydride or halosuccinicanhydride or succinic ester (U.S. Pat. No. 2,568,876). In branchedolefins, particularly branched polyolefins, R may be hydrogen, methyl ora long chain hydrocarbyl group. However, the exact structure may notalways be ascertained and the various R groups cannot always beprecisely defined in the Ene products from polyolefins and maleicanhydride.

Suitable olefins include butene, isobutene, pentene, decene, dodecene,tetradecene, hexadecene, octadecene, eicosene, and polymers ofpropylene, butene, isobutene, pentene, decene and the like, andhalogen-containing olefins. The olefins may also contain cycloalkyl andaromatic groups. The most preferred alkenyl succinic anhydrides used inthis invention are those in which the alkenyl group contains a total offrom 4 to 400 carbon atoms; from 4 to about 20 carbon atoms for aqueoussystems; and at least 8 to 400 and more preferably 10 to 300 forhydrocarbon systems.

Many of these hydrocarbyl substituted dicarboxylic acid materials andtheir preparation are well known in the art as well as beingcommercially available, e.g., 2-octadecenyl succinic anhydride andpolyisobutenyl succinic anhydride.

With 2-chloromaleic anhydride and related acylating agents,alkenylmaleic anhydride reactants are formed. Lactonization of theseproducts also afford useful precursors to lactone oxazoline products.

Preferred olefin polymers for reaction with the unsaturated dicarboxylicacids are polymers comprising a major molar amount of C₂ to C₅monoolefin, e.g., ethylene, propylene, butylene, isobutylene andpentene. The polymers can be homopolymers such as polyisobutylene, aswell as copolymers of two or more of such olefins such as copolymers of:ethylene and propylene; butylene and isobutylene; propylene andisobutylene; etc. Other copolymers include those in which a minor molaramount of the copolymer monomers, e.g., 1 to 20 mole % is a C₄ to C₁₈non-conjugated diolefin, e.g., a copolymer of isobutylene and butadiene;or a copolymer of ethylene, propylene and 1,4-hexadiene; etc.

The olefin polymers will usually have number average molecular weightswithin the range of about 750 and about 200,000, more usually betweenabout 1000 and about 20,000. Particularly useful olefin polymers havenumber average molecular weights within the range of about 900 and about3000 with approximately one terminal double bond per polymer chain. Anespecially valuable starting material for a highly potent dispersantadditive are polyalkenes e.g. polyisobutylene, having up to 10,000carbons.

Especially useful when it is desired that the dispersant additives alsopossess viscosity index improving properties are 5,000 to 200,000, e.g.,25,000 to 100,000 number average molecular weight polymers. Anespecially preferred example of such a V.I. improving polymer is acopolymer of about 30 to 85 mole % ethylene, about 15 to 70 mole % C₃ toC₅ mono-alpha-olefin, preferably propylene, and 0 to 20 mole % of a C₄to C₁₄ non-conjugated diene.

These ethylene-propylene V.I. improving copolymers or terpolymers areusually prepared by Ziegler-Natta synthesis methods, e.g., see U.S. Pat.No. 3,551,336. Some of these copolymers and terpolymers are commerciallyavailable, such as VISTALON^(R), an elastomeric terpolymer of ethylene,propylene and 5-ethylidene norbornene, marketed by Exxon Chemical Co.,New York, N.Y. and NORDEL^(R), a terpolymer of ethylene, propylene and1,4-hexadiene marketed by E. I. duPont de Nemours & Co.

Unsubstituted or simple lactone reactants (Y═H) are readily obtained bythe acid-catalyzed lactonization of an alkenyl dicarboxylic acid analog,the latter being derived from the ring scission of an alkenyl succinicanhydride with water, an alcohol or an amine as shown below wherein HQrepresents water, alcohols containing from 1 to 10 carbons and dialkylamines containing from 2 to 10 carbons and R is as previously defined.##STR5##

The reaction with HQ is assumed to open the anhydride at the leastcongested carbonyl group and form a succinic acid, hemi-ester or amicacid product which in the presence of an acid catalyst cyclizes mostlyto the 5-ring lactone product as shown above.

It is possible to use alkenyl substituents with the double bond in the1, 2, or 3-position or even double bonds further out on the hydrocarbylchain since the acid catalyst is capable of moving it into a positionsuitable for lactone formation. In general, the size of the lactone ringformed will depend upon, inter alia, the position of the double bond,and which carboxylic acid group participates in the lactone formingreaction. As a consequence, both 5- and 6-ring (or larger ring) lactonescan be envisaged as illustrated below: ##STR6## For convenience, theproducts of the present invention are usually shown as 5-ring lactonesalthough larger ring lactone products can also be present.

LACTONIZATION CATALYSTS

The intramolecular cyclization step involved in the process of thisinvention must be carried out in the presence of an acid-type catalystin order to effect formation of the lactone. Suitable catalysts includethe mineral acids such as hydrochloric acid, sulfuric acid, perchloricacid, and phosphoric acid; the sulfonic acids such as the alkanesulfonicacids and the arylsulfonic acids; the Lewis type acids such as aluminumchloride, boron trifluoride, antimony trichloride, and titaniumtetrachloride; low molecular weight sulfonic acid type ion exchangeresin materials, such as cross-linked sulfonated polystyrene which iscommercially available as Dowex-50. The alkanesulfonic acid catalystsare preferably the lower alkanesulfonic acids containing from 1 to 12carbon atoms, for example, methanesulfonic acid, ethanesulfonic acid,propanesulfonic acid, and butanesulfonic acid. If desired, a mixture oflower alkanesulfonic acids can be used and such a mixture containingmethane, ethane, and propanesulfonic acids is commercially available.Ordinarily, the alkanesulfonic acid will comprise from 92% to 95%sulfonic acid, from 1 to 2% sulfuric acid, and from 3 to 6% water. Thearylsulfonic acid catalyst which can be used in the process includes thebenzenesulfonic acids, toluenesulfonic acid, and chlorobenzenesulfonicacids, with p-toluenesulfonic acid and 4-chloro-benzenesulfonic acidbeing preferred. The amount of catalyst present in the reaction zone canbe varied over wide limits depending upon the nature of the reactantsand the catalyst used. The amount of catalyst used is also determined toa considerable extent by the temperature selected for conducting thereaction. Thus, at higher temperatures the amount of catalyst requiredin the reaction is less than when lower temperatures are used and theuse of excessive amounts of catalyst at the more elevated temperatureswill promote the formation of undesired side products. Ordinarily, theamount of catalyst used will be between about 0.1% up to 10% by weightof the amount of the alkenyl succinic anhydride reactant.

SUBSTITUTED LACTONE REACTANTS

The presence of certain heteroatoms adjacent to the novel lactoneoxazoline ring combination oftimes endows the novel lactone oxazolinesystem with other desirable properties such an antioxidation andanticorrosion activity. In the present invention, we have devised novelways of introducing hydroxyl, thiyl, sulfide, sulfoxide, sulfone andsulfo groups adjacent to the lactone oxazoline functions as describedbelow:

HYDROXYL LACTONE AND EPOXY REACTANTS

Hydroxyl containing lactone reactants are prepared via the addition ofperacids, hydrocarbyl peroxides or aqueous hydrogen peroxide to alkenylsuccinic acid hemiester or amide reagents as shown below: ##STR7##wherein Q is as previously defined and R' represents hydrogen, acylgroup containing from 2 to 20 carbons or alkyl group containing from 2to 20 carbons. As an alternate, the epoxidation of alkenyl succinicanhydride, with peracids gives epoxy anhydrides which can react with (1)water, alcohols or amines to generate the desired hydroxy-substitutedlactone reactants or (2) directly with THAM to give the lactoneoxazoline end-products.

The thiyl substituted lactones can be conveniently prepared via (1)thiol-induced scission of ring epoxy anhydrides as shown below wherein Trepresents alkyl, aryl or heterocyclic groups containing from 1 to 50carbons ##STR8## or via (2) sulfenyl halide addition to the double bondin alkenyl succinic acids or esters followed by lactonization via aninternal displacement of halide as shown below: ##STR9## wherein T isdefined as above.

The type of thiyl substituted lactone product will depend upon (i) themode of ring cleavage by the thiol reagent and (ii) the mode of additionof the sulfenyl chloride to the double bond in the alkenyl succinicacid, ester or amide reactant.

With sulfur halides (S_(x) Cl₂, where x is 1-4), thio, dithio andpolythio bis-lactones are formed. Subsequent reaction of the latter withTHAM affords the corresponding thio-bis-lactone oxazoline products.

Oxidation of the mono-thio-bis-lactones with peroxides can yield bothsulfoxides and sulfones. In the case of the dithio-bis-lactones,oxidation affords sulfocontaining lactones.

In another approach thiyl lactones can also be designed by addition ofthe sulfenyl chloride reagent to the alkenyl succinic anhydride.Lactonization of the adduct can then be effected by either reacting (i)the sulfenyl chloride adduct per se, or (ii) the dehydrohalogenatedadduct with an alcohol, water or an amine. Lactonization of thedehydrohalogenated thiyl substituted anhydride via option (ii) ispreferably conducted in the presence of an acid catalyst.

Examples of useful thiols in preparing thiyl lactones via epoxidecleavage include alkyl and aryl thiols and heterocyclic thiols such as2-mercapto-benzothiazole. Dithiophosphoric acids e.g. (RO)₂ P(S═S)--SH,are also useful in designing phosphorus-containing products. In analternate synthetic approach, the sulfenyl chloride analogs of theabove-described thiols can be added to alkenyl succinic acid analogs togive the desired thiyl-substituted lactone reagents.

In another embodiment of the present invention, the reaction ofchlorosulfonic acid or its equivalent, e.g. SO₃ and its complexes, withalkenylsuccinic anhydrides gives adducts which upon hydration yieldsulfo lactone acids. Treatment of the latter with THAM can undersuitable conditions generate sulfo lactone oxazoline end-products.

In still another embodiment, lactam carboxylic acids are used in thedesign of lactam oxazoline additives.

THE AMINO ALCOHOL

The amino alcohol used to react with the lactone to provide theoxazoline ring is a 2,2-disubstituted-2-amino-1-alkanol containing atotal of 4 to 8 carbon atoms, and which can be represented by theformula: ##STR10## wherein X is hydrogen, an alkyl, e.g. C₁ to C₃ alkyl,or hydroxy alkyl group, with at least one of the X substituents, andpreferably both of the X substituents, being a hydroxy alkyl group, withat least one of the X substituents, and preferably both of the Xsubstituents being a hydroxy alkyl group of the structure --(CH₂)_(n)OH, wherein n is 1 to 3.

Examples of such 2,2-disubstituted amino alkanols, include2-amino-2-methyl-1,3-propanediol,2-amino-2-(hydroxymethyl)-l,3-propanediol (also known astris-hydroxyaminomethane or THAM), 2-amino-2-ethyl-1,3-propanediol, etc.Because of its effectiveness availability, and cost, the THAM isparticularly preferred.

By sharp contrast, we have found that other amino alcohols such asethanolamine, propanolamine and butanolamine which lack2,2-disubstitution, do not afford oxazoline products. Similarly, theprior art (British Pat. No. 1,420,962) clearly teaches that ethanolaminereacts with lactone acids to give amide derivatives via cleavage of thelactone ring. We have discovered that interaction of lactone acids,esters and amides with 2,2-disubstituted amino alcohols is unique, inthat the lactone ring of the reactant remains intact and novel lactoneoxazoline products are formed exclusively.

THE OXAZOLINE REACTION CONDITIONS

The formation of the novel oxazoline materials in a very high yield, canbe effected by adding at least about 1 molar equivalent of the aforesaid2,2-disubstituted-2-amino-1-alkanol per mole equivalent of the polyalkyllactone acid, ester or amide with or without an inert diluent, andheating the mixture at 100°-240° C., preferably 170°-220° C. untilreaction is complete by infra-red analysis of the product showingmaximal absorption for oxazoline.

Although not necessary, the presence of small amounts such as 0.01 to 2wt. %, preferably 0.1 to 1 wt. %, based on the weight of the reactants,of a metal salt can be used in the reaction mixture as a catalyst. Themetal catalyst can later be removed by filtration or by washing ahydrocarbon solution of the product with a lower alcohol, such asmethanol, ethanol, isopropanol, etc., or an alcohol/water solution.

Alternatively, the metal salt can be left in the reaction mixture, as itappears to become stably dispersed, or dissolved, in the reactionproduct, and depending on the metal, it may even contribute performancebenefits to the oil or gasoline. This is believed to occur with the useof zinc catalysts in lubricants.

Inert solvents which may be used in the above reaction includehydrocarbon oils, e.g. mineral lubricating oil, kerosene, neutralmineral oils, xylene, halogenated hydrocarbons, e.g., carbontetrachloride, dichlorobenzene, tetrahydrofuran, etc.

Metal salts that may be used as catalysts in the invention includecarboxylic acid salts of Zn, Co, Mn and Fe. Metal catalysts derived fromstrong acids (HCl, sulfonic acid, H₂ SO₄, HNO₃, etc.) and bases, tend todiminish the yield of the oxazoline products and instead favor imide orester formation. For this reason, these strong acid catalysts or basiccatalysts are not preferred and usually will be avoided. The carboxylicacids used to prepare the desired catalysts, include C₁ to C₁₈, e.g., C₁to C₈ acids, such as the saturated or unsaturated mono- and dicarboxylicaliphatic hydrocarbon acids, particularly fatty acids. Specific examplesof such desired carboxylic acid salts include zinc acetate, zincformate, zinc propionate, zinc stearate, manganese(ous) acetate, irontartrate, cobalt(ous) acetate, etc. Completion of the oxazoline reactioncan be readily ascertained by using periodic infrared spectral analysisfor following oxazoline formation (C═N absorption band at 6.0 microns)until maximized relative to lactone absorption or by the cessation ofwater evolution.

REACTION MECHANISM OF THE OXAZOLINE FORMATION

While not known with complete certainty, but based on experimentalevidence, it is believed that the reaction of the alkyl lactonematerial, e.g, a substituted lactone acid, ester or amide with the aminoalcohol of the invention, e.g. 1 to 1.5 molar equivalents of2,2-disubstituted-2-aminoethanol such as tris-hydroxymethylamino methane(THAM), gives lactone oxazoline ring structures as portrayed above.

USE OF THE POLYALKYL LACTONE-OXAZOLINE ADDITIVE IN OLEAGINOUSCOMPOSITIONS

The oil-soluble lactone oxazoline reaction products of the invention canbe incorporated in a wide variety of oleaginous compositions. They canbe used in lubricating oil compositions, such as automotive crankcaselubricating oils, automatic transmission fluids, etc. in concentrationsgenerally within the range of about 0.01 to 20 weight percent, e.g. 0.1to 10 weight percent, preferably 0.3 to 3.0 weight percent, of the totalcomposition. The lubricants to which the lactone-oxazoline products canbe added include not only hydrocarbon oils derived from petroleum butalso include synthetic lubricating oils such as polyethylene oils; alkylesters of dicarboxylic acid; complex esters of dicarboxylic acid,polyglycol and alcohol; alkyl esters of carbonic or phosphoric acids;polysilicones; fluorohydrocarbon oils; mixtures of mineral lubricatingoil and synthetic oils in any proportion, etc.

When the products of this invention are used as multifunctionaladditives having detergency and, anti-rust properties in petroleum fuelssuch as gasoline, kerosene, diesel fuels, No. 2 fuel oil and othermiddle distillates, a concentration of the additive in the fuel in therange of 0.001 to 0.5 weight percent, based on the weight of the totalcomposition, will usually be employed.

When used as an antifoulant in oil streams in refinery operations toprevent fouling of process equipment such as heat exchangers or inturbine oils, about 0.001 to 2 wt. % will generally be used.

The additive may be conveniently dispensed as a concentrate comprising aproportion of the additive, e.g., 20 to 90 parts by weight, dissolved ina proportion of a mineral lubricating oil, e.g., 10 to 80 parts byweight, with or without other additives being present.

In the above compositions or concentrates, other conventional additivesmay also be present including dyes, pour point depressants, antiwearagents such as tricresyl phosphate or zinc dialkyldithiophosphates of 3to 8 carbon atoms in each alkyl group, antioxidants, such as N-phenylα-naphthylamine, tert-octylphenol sulfide, 4,4'-methylenebis(2,6-di-tert-butyl phenol), viscosity index improvers such asethylene-propylene copolymers, polymethacrylates, polyisobutylene, alkylfumarate-vinyl acetate copolymers and the like, de-emulsifiers such aspolysiloxanes, ethoxylated polymers and the like.

This invention will be further understood by reference to the followingexamples, which include preferred embodiments of the invention.

SIMPLE LACTONE REACTANTS Example 1 (DIBSALAC)

Thirty grams (0.143 mole) of diisobutenyl succinic anhydride (DIBSA)which can be a mixture of three isomers (A, B, and C), depending on themode of synthesis, were combined ##STR11## with 2.6 g of water and threedrops of concentrated sulfuric acid. The mixture was heated to 110°-120°C. for one hour. Infrared analysis of the reaction mixture showed thatlactone formation was virtually complete. The addition of 200 ml ofether and subsequent cooling of the resulting ether solution causedsolids to separate from solution. Three crops of while solid amountingto 27.1 g were collected and recrystallized from ether-acetone solution.The product, m.p. 141°-142° C., featured an IR spectrum with intensecarbonyl absorption bands at 5.70 (lactone) and 5.82 (carboxylic acid)microns and analyzed for 62.78% C and 9.14% H (Theory: 63.13% C and8.86% H). The product, dibsalac, presumably could be one or more of theisomeric lactones depicted below. The proton and IR spectral datasuggest that the 5-ring lactone acid products ##STR12## predominate whenreactant A is employed in the lactonization process.

Example 2 (NOSALAC)

One mole (210 g) of n-2-octenylsuccinic anhydride (nosa) and 1.1 mole(20 g) of water were combined and heated at 100°-110° C. for about ahalf hour. A quantitative conversion to n-2-octenylsuccinic acidoccurred. Five drops of concentrated sulfuric acid were added to thelatter, and the mixture was then heated for 16 hours at about 155° C.Upon cooling, the liquid product gradually crystallized. The whitesolids, m.p. 94°-95° C., were isolated in high yield and featured an IRspectrum with strong absorption bands at 5.65 and 5.82 microns. Thelactone acid analyzed for 63.49% C and 8.35% H, and judging from its IRspectrum (carbonyl absorption at 5.65 microns) is mainly a 5-ringlactone although some 6-ring lactone products can also form dependingupon reaction conditions. Plausible lactone structures (for nosalac) arefeatured below: ##STR13##

Example 3 (TPSALAC)

A mixture of 405 g (1.52 moles) of tetrapropenylsuccinic anhydride(TPSA) and 30 g (1.66 moles) of water were heated to 100°-110° C. for ahalf hour. Infrared analysis of the reaction mixture indicated completeconversion of the anhydride to tetrapropenylsuccinic acid.

The mixture was treated with 40 g of Amberlyst 15 catalyst and heated to125°-130° C. overnight. Infrared analysis indicated that lactonizationwas complete. The lactone acid product was dissolved in ether andfiltered to remove the catalyst. Rotoevaporation of the supernatant gavean oily concentrate which featured an IR spectrum with intense lactoneand carboxylic acid carbonyl absorption bands.

Example 4 (OSALAC)

A half mole (175 g) of 2-octadecenyl succinic anhydride (osa) and 0.55mole (10 g) of water were mixed and heated in a reaction flask for ahalf hour at 80° C. Infrared analysis showed that complete conversion ofthe anhydride to succinic acid had occurred. While stirring at 80° C.,0.5 g of concentration sulfuric acid was added, and the reactiontemperature was increased to 130°-140° C. Heating at 140° C. for 1.5hours completely converted the dicarboxylic acid to the desired lactoneacid products. When the cooled mixture was diluted with ether a whitesolid separated from solution. Infrared analysis of the isolated solidsrevealed the presence of a 5-ring lactone acid (strong bands at 5.67 and5.82 microns). Cooling the supernatant gave more solids. Furtherfractional crystallization of later crops afforded 6-ring lactone acidproducts. The combined weight of all crops revealed that the yield oflactone acid product was quantitative. A recrystallized sample of 5-ringlactone product melted at 112° C. and analyzed for 71.50% carbon, 10.77%H and 16.67% oxygen. Theory requires 71.49% C, 11.18% H, and 17.32% O.

Example 5 (PIBSALAC)

One hundred twenty grams of polisobutenyl succinic anhydride (pibsa) ofMW≈960 and having a saponification number (Sap. No.) of 92 were dilutedin 100 ml of tetrahydrofuran (THF). Two grams of water were added andthe resulting mixture was heated to reflux temperature for about twohours. Infrared analyses of the mixture showed that the anhydride wasfully converted to the succinic acid analog. The THF solvent was boiledoff and 1 ml of concentrated sulfuric acid was added to the mixture atabout 110° C. Heating for two hours at 120° C. effected the conversionof the polyisobutenyl succinic acid to the desired lactone acid product.Infrared analyses showed the presence of strong absorption bands atabout 6.5-8.5 microns.

The mixture was diluted in 200 ml of hexane, washed twice with 200 ml ofwater and subsequently concentrated by rotoevaporation for two hours at80° C. Infrared analysis of the lactone acid product treated withdiethylamine featured an intense absorption band at 5.64 microns (5-ringlactone carbonyl stretching).

Example 6 (PIBSALAC)

A mixture of one hundred grams of polyisobutenyl succinic acid asprepared in Example 5 and 10 g of Amberlyst 15 catalyst were heated atabout 100° C. for about eight hours, and then at 120° C. for a halfhour. Infrared analysis showed the presence of lactone acid. The productwas diluted with hexane, filtered, and rotoevaporated at 80° C. for fourhours. The residue upon treatment with an excess of diethylaminefeatured an infrared spectrum with a strong lactone carbonyl absorptionband at 5.64 microns.

Example 7 (PIBSALAC)

A mixture of 140 g (0.1 mole) of polyisobutenyl succinic anhydride(MW≈960 and having a saponification number [Sap. No. ] of 92), 3 g ofwater and 1 g of concentrated sulfuric acid were heated for about threehours at 105° C. Infrared analysis indicated that the anhydride wasdirectly and completely converted to the desired lactone acid asevidenced by the strong carbonyl absorption bands at 5.63 to 5.84microns. The reaction product was treated with 0.02 mole of NaOH(dissolved in tetrahydrofuran) filtered and rotoevaporated at 80° C. forfour hours. The IR spectrum of the amber concentrate treated with anexcess of diethylamine showed a strong lactone carbonyl absorption at5.65 microns.

Example 8 (NOSALAC ESTER)

A half-mole (105 g) of n-octenylsuccinic anhydride and 23 g of absoluteethanol were combined and gradually heated to 100° C. over a half-hourperiod. A milliliter of concentrated sulfuric acid was added and heatingat 120° C. was continued for 30 hours. Infrared analysis indicatedvirtually complete conversion to lactone ester. Upon standing, theproduct partially solidified. Recrystallization of the crude solid fromhexane afforded a crystalline material, m.p. 83° C., which featured aninfrared spectrum with intense lactone and ester carbonyl absorptionbands at 5.63 and 5.80 mircons.

Example 9 (DIBSALAC AMIDE)

The dropwise addition of a tenth mole (7.3 g) of diethylamine to 0.1mole (21 g) of diisobutenylsuccinic anhydride in 100 ml of ether gavethe amic acid directly. Three drops of concentrated sulfuric acid wasadded to the reaction mixture which was freed of ether solvent andheated to about 200° C. for 10 hours. Infrared analysis revealed thepresence of lactone amide. The produce was diluted in ether and washedwith aqueous Na₂ CO₃. The ether solution was dried over solid Na₂ SO₃and rotoevaporated.

Distillation of a portion of the concentrated product gave a fraction,b.p. 170° C. (0.1 mm), which featured an infrared spectrum with verystrong absorption bands at 5.62 (lactone) and 6.08 (amide) microns, andanalyzed for 4.90% nitrogen. Theory required 4.94% nitrogen.

Example 10 (NOSALAC AMIDE)

Twenty-eight grams of the lactone acid product prepared in Example 2(mainly n-hexyl butyrolactone-α-acetic acid) were treated with an excessof gaseous ammonia at 180° C. for about two hours. The product wasdissolved in hot xylene and filtered. Upon cooling the solution, a solidproduct precipitated. The dried product (15 g) melted at 117°-119° C.,showed an IR spectrum with dominant bands at 5.65 and 6.0 microns andanalyzed for 62.75% C, 9.29% H and 6.18% N. Theory for the lactone amiderequires 63.40% C, 9.31% H and 6.18% N.

EPOXY ANHYDRIDE REACTANTS Example 11 (EPOXY-DIBSA)

Gram portions of 0.05 mole of meta-chloroperbenzoic acid (70% purity)were added over a half-hour period to 0.05 mole (10.1 g) ofdiisobutenylsuccinic anhydride dissolved in 300 ml of methylene chloridemaintained at 0° C. As the mixture warmed to room temperature, it becameclear and then clouded as m-chlorobenzoic acid byproduct separated fromthe solution. The mixture was stirred overnight at room temperature. Themixture was filtered, and the supernatant was washed with a 5% aqueousNa₂ CO₃ solution twice, dried over Na₂ SO₄, and concentrated byrotoevaporation. During evaporation, a solid separated from solution.The white solid (9.4 g) melted at 94°-97° C. and analyzed for 7.9%oxygen (theory required 8.01% oxygen). The spectral data were consistentwith ##STR14##

Example 12 (EPOXY PIBSA)

Approximately 0.2 mole (240 g) of polyisobutenylsuccinic anhydride(MW≈960) having a saponification number of approximately 84 wasdissolved in one liter of CH₂ Cl₂ at 25° C., the well-stirred solutionwas treated with 5 g portions of 0.2 mole (40.6 g) of m-chloroperbenzoicacid over an hour period. An exothermic reaction ensued, and raised thetemperature of the reaction mixture to 34° C. Upon standing overnight,m-chlorobenzoic acid separated from solution. Filtration gave a clearCH₂ Cl₂ solution which was washed with aqueous 5% Na₂ CO₃ solution, anddistilled water, and then dried over CaCl₂. Rotoevaporation at 70° C.for two hours afforded 242 g of epoxy PIBSA as an amber oil.

Example 13 (EPOXY PIBSA)

Two hundred grams of polyisobutenylsuccinic anhydride of MW≈1300 havinga saponification number of about 100 were dissolved in a liter of CH₂Cl₂ and 40.5 g (0.2 mole) of m-chloroperbenzoic acid (85%) were addedportionwise over an hour period to the well-stirred reaction mixture atroom temperature. The exothermic reaction caused the temperature of themixture to peak to 33° C. The clear solution was allowed to stir atambient temperature for five hours. During this period, white solidsseparated from solution. The solids were removed by filtration, and thesupernatant was freed of CH₂ Cl₂, and diluted in hexane and filtered.Rotoevaporation at 80° C. for two hours gave a concentrate (180 g) whichwas diluted in 90 g of neutral oil.

HYDROXYL-CONTAINING LACTONE REACTANTS Example 14 (HYDROXY DIBSALAC)

A mixture of ca. 0.01 mole (2.76 g) of epoxy dibsa as described inExample 11 and 0.2 g of H₂ O was dissolved in 5 ml of tetrahydrofuran(THF) and heated to reflux for an hour. IR analysis indicates completeconversion of the epoxy anhydride to 5- and 6-ring hydroxy lactonecarboxylic acids: ##STR15##

The synthesis of the latter was also achieved by simply combiningequimolar amounts (0.1 mole) of dibsa, hydrogen peroxide (30%) and acatalytic amount of sulfuric acid (1 drop) in 100 ml tetrahydrofuran(THF) and refluxing the mixture for several hours.

Addition of ether to the reaction mixture induced the separation ofsolid product. Filtration gave a solid which featured an infraredspectrum with intense lactone and carbonyl absorption bands.Recrystallization from ether gave a solid which melted at 180° C. andanalyzed for 59.29% carbon, 8.28% hydrogen and 32.57% oxygen. Theory forthe hydroxy lactone carboxylic acid requires 59.00% C, 8.27% H and32.75% O.

Example 15 (HYDROXY PIBSALAC)

A mixture comprising 0.32 mole (410 g) of pibsa (MW≈960) with asaponification number of 83, 0.32 mole (36.3 g) hydrogen peroxide (30%aqueous solution) and 0.4 g (0.1 wt.% of concentrated sulfuric acid washeated with stirring at about 120° C. for approximately five hours.Infrared analysis showed the presence of carbonyl bands ascribable tolactone acid. The product was diluted with an equal volume of neutraloil.

Example 16 (HYDROXY DIBSALAC ESTER)

A tenth mole (22.6 g) of monomethyl diisobutenyl succinate and 0.1 mole(11.4 g) of 30% hydrogen peroxide were combined with 4.6 g of formicacid and heated to about 50° C. with stirring. Infrared analysis of thereaction mixture after two hours reaction at 50° revealed that thehemi-ester was completely converted to the desired hydroxyl containinglactone ester. The same ester was also obtained by (i) epoxidation ofmono-methyl diisobutenyl succinate with m-chloroperbenzoic acid or (ii)methanolysis of epoxy dibsa prepared in Example 11. The proposedstructure for the major hydroxylcontaining lactone ester generated viathe three synthetic schemes is methylα-neo-pentyl-α-hydroxymethylbutyrolactone-α-acetate: ##STR16##

Treatment of the latter with an equimolar portion of morpholine gave aproduct which featured an IR spectrum identical to that for the hydroxylactone amide obtained in Example 19.

Example 17 (HYDROXY PIBSALAC ESTER)

A tenth mole (121 g) of epoxy pibsa prepared in Example 12 and 0.1 mole(13.4 g) of n-octanol were heated together for about 12 hours. Theproduct was diluted with an equal weight of neutral oil and filtered.The infrared spectrum of the oil-diluted product featured the expectedlactone and ester carbonyl absorptions at 5.62 and 5.74 microns.

Example 18 (HYDROXY DIBSALAC AMIDE)

An ether solution of 0.01 mole (0.87 g) of morpholine was added dropwiseto an ether solution of 0.01 mole (2.26 g) of epoxy dibsa (Example 11)at about 25° C. The addition was exothermic and caused the ether toreflux during addition. Upon cooling, solids formed. Infrared analysisof the isolated solid (0.4 g) showed sharp bands at 3.03 (hydroxyl),5.80 (lactone) and 6.08 (amide) microns indicative of thehydroxylcontaining 6-ring lactone amide. The residue from thesupernatant (ca. 2.4 g) featured an IR spectrum consistent with the5-ring lactone product. The solid product m.p. 94-97 analyzed for 62.07%C, 8.60% H, and 4.74% N. Theory for the hydroxy lactone amide requires61.32% C, 8.69% H, and 4.47% N.

ExaMPLE 19 (HYDROXY PIBSALAC AMIDE)

A tenth mole (121 g) of epoxy pibsa prepared in Example 12 was dissolvedin 100 ml of CH₂ Cl₂, and 0.1 mole (9.0 g) of morpholine was added to itdropwise. The addition was exothermic. The mixture was then heated at80° C. for 12 hours, and at 130° C. for an additional 6 hours. Theproduct analyzed for 0.83% N, and feature an IR spectrum with prominentbands at 5.61 and 6.02 microns as expected for a lactone amide.

THIYL-SUBSTITUTED LACTONE REACTANTS Example 20 (ADDUCT OF SCl₂ ANDn-OCTENYLSUCCINIC ANHYDRIDE)

Three moles (630 g) of n-octenylsuccinic anhydride were diluted in aliter of CH₂ Cl₂ and stirred at room temperature. Then 1.5 moles (154 g)of SCl₂ in 500 ml of CH₂ Cl₂ were added dropwise. The exothermicreaction peaked to 50° C. initially and external cooling was applied tomaintain reaction temperature at about 25° C. No HCl evolution occurred.After stirring the reaction mixture for an hour after the SCl₂ addition,the solvent was removed by evaporation with a mild stream of nitrogen.The solid that separated from solution during solvent evaporation wasisolated (40 g) and after being recrystallized from CH₂ Cl₂, melted at149°-150° C. and analyzed for 55.45% C, 7.17% H, 5.73% S and 11.4% Cl.The adduct, C₂₄ H₂₆ O₆ SCl₂ requires 55.06% C, 6.93% H, 6.13% S, and13.55% Cl. The infrared spectrum featured an intense anhydrideabsorption at 5.67 microns, and a proton spectrum was consistent withthe structure shown below.

The concentrate obtained from the supernatant weighed 745 g and featuredan IR spectrum similar to that shown for the solid. The yield of adductwas virtually quantitative. One possible structure shown below.##STR17##

Example 21 (S₂ Cl₂ -n-OCTENYLSUCCINIC ANHYDRIDE ADDUCT)

A mole (210 g) of n-octenylsuccinic anhydride was dissolved in a literof ether and a half mole (67.5 g) of sulfur monochloride (S₂ Cl₂) wasadded dropwise to the stirred solution at room temperature. Anexothermic reaction occurred and the addition was completed underrefluxing conditions. The reaction mixture was stirred overnight andthen concentrated by rotoevaporation at 50° C. for 2 hours. The productfeatured an IR spectrum with a prominent anhydride carbonyl band at 5.65microns, and analyzed for 49.33% C, 6.04% H, 10.7% S and 12.6% Cl.Theory for the S₂ Cl₂ -n-octenylsuccinic anhydride adduct (C₂₄ H₃₆ Cl₂O₆ S₂) requires 51.88% C, 6.53% H, 11.54% S, and 12.76% Cl.

Example 22

Two-tenths (30.4 g) mole of cis-1,2,3,6-tetrahydrophthalic anhydride(cis-4-cyclohexene-1,2-dicarboxylic anhydride) was dissolved inchloroform (200 ml) and 0.1 mole (10.3 g) of SCl₂ were added dropwise tothe well stirred solution at room temperature. The SCl₂ additionincreased the temperature to 53° C. and the addition was completed atabout 53° C. Midway during SCl₂ addition the solution turned hazy andsome solids separated from solution. After addition the mixture wasallowed to cool and the solids (20 g) were isolated by filtration. Thesolid product featured an IR spectrum with strong anhydride carbonylabsorption, melted at 177°-178° C., and analyzed for 46.88% C, 4.22% C,7.68% S, and 14.93% Cl. Theory for the adduct (C₁₆ H₁₆ Cl₂ O₆ S)requires 47.18% C, 3.96% H, 7.87% S, and 17.41% Cl.

Example 23 (THIO-BIS-OSALAC)

Two-tenths mole (73.6 g) of octadecenyl succinic acid was dissolved in500 ml ether and a tenth mole (10.3 g) of SCl₂ was added dropwise to thestirred ether solution at about 25° C. The addition was exothermic(ether refluxed) and HCl evolution occurred. The mixture was refluxedfor about 8 hours. Upon cooling solids separated from solution. Thesolid product featured an infrared spectrum with prominent lactone andcarboxylic acid carbonyl absorptions at 5.62 and 5.82 microns, melted at158°-163°, and analyzed for 69.01% C, 10.17% H, 4.37% S and 16.74% O.Theory for the lactone acid (C₄₄ H₇₈ O₈ S) requires 68.88% C, 10.25% H,4.18% S and 16.69% O.

Further refluxing the supernatant gave four more crops of product with acombined weight of 50 g. The yields were quantitative. The proposedstructure for thio-bis-osalac is illustrated below. ##STR18##

Example 24 (DITHIO-BIS-OSALAC)

Two hundred grams (0.54 mole) of n-octadecenyl succinic acid weredissolved in a liter of CHCl₃ and 36.7 g (0.272 mole) of sulfurmonochloride (S₂ Cl₂) were added dropwise to the stirred solution atroom temperature. The exothermic process was accompanied by vigorous HClevolution. After refluxing the mixture for about eight hours, thesolution was cooled and solids separated. Filtration gave 19 g of solid(m.p. 131°-136° C.) which featured an IR spectrum with intense carbonylbands at 5.62 and 5.72 microns, and analyzed for 66.42% C, 9.63% H, and8.22% S. Theory for the adduct (C₄₄ H₇₈ O₈ S₂) requires 66.12% C, 9.84%H, and 8.02% S. Rotoevaporation of the supernatant gave a solid productin high yield. The proposed structure for dithio-bis-osalac is givenbelow. ##STR19##

Example 25 (THIO-BIS-DIBSALAC)

Two tenths mole (42.0 g) of dibsa was dissolved in 100 ml. of THF and0.1 mole (10.3 g) of SCl₂ were added. During addition the reactiontemperature climbed to about 35° C. and HCl evolution occurred. Themixture was refluxed for four hours and then heated to 100° (THFdistilled off) for two more hours to effect completedehydrohalogenation.

The residue was cooled and dissolved in THF and 0.2 mole of water andtwo drops of concentrated sulfuric acid were added. The mixture wasrefluxed for several hours. Infrared analysis revealed completeconversion to the desired thio-bis-lactone acid.

Example 26 (THIO-BIS-PIBSALAC)

Approximately 130 g of polyisobutenylsuccinic acid (MW≈960 (prepared viahydrolysis of PIBSA having a saponification number of ca 84) weredissolved in 400 ml of chloroform and 0.05 mole (5.3 g) of SCl₂ wasadded dropwise to the stirred solution. After refluxing the mixtureovernight, two drops of sulfuric acid were added, the solvent wasstripped off, and the mixture heated at about 100° C. overnight. Theproduct featured an infrared spectrum with strong absorption bands inthe 5.6-5.8 micron region and analyzed for 1.69% sulfur and 0.09%chlorine. The IR spectrum of the diethylamine-treated product revealed astrong lactone carbonyl band at 5.63 microns.

Example 27 (THIO-BIS-PIBSALAC)

A tenth mole (130 g) of polyisobutenylsuccinic anhydride (MW≈960) havinga saponification number of approximately 84 was dissolved in 100 ml ofdioxane and 0.05 mole (5.3 g) of SCl₂ were added dropwise to thewell-stirred solution at ca 25° C. The mixture was then refluxed forfour hours (HCl evolution noted). At this point, 4 g of water acidifiedwith three drops of concentrated sulfuric acid were added and themixture was further refluxed for 24 hours. The mixture was filteredthrough basic celite and rotoevaporated at 90° C. for several hours. Theconcentrate featured an IR spectrum with strong absorption bands in the5.6-5.8 micron region, and analyzed for 1.55% sulfur and 0.09% chlorine.

Example 28 (THIO-BIS-NOSALAC ESTER)

A half mole of the adduct of SCl₂ and n-octenylsuccinic anhydridedescribed in Example 20 was added to 500 ml of xylene containing 32 g ofmethanol. The mixture was allowed to stir overnight and heated to refluxfor about four hours. The product was then rotoevaported for three hoursat 70°-80° C. The final product featured an IR spectrum with intenselactone and ester carbonyl absorption at 5.63 and 5.78 microns, andanalyzed for 60.48% carbon, 8.30% hydrogen, and 6.48% sulfur. Thethio-bis-lactone ester (C₂₆ H₄₂)₈ S) requires 60.67% C, 8.23% H and6.23% S.

The same ester lactone was easily prepared via the addition of SCl₂ tothe mono-methyl ester of n-octenyl succinic acid.

Example 29 (DITHIO-BIS-NOSALAC ESTER)

Four-tenths mole of the adduct of S₂ Cl₂ and n-octenylsuccinic anhydridedescribed in Example 21 and 0.8 mole (25.6 g) of methanol were dissolvedin 200 ml of chloroform and stirred at room temperature for four days,refluxed for 16 hours, and roto-evaporated at 80° C. for three hours.The product showed an IR spectrum with intense lactone and estercarbonyl bands and analyzed for 57.19% carbon, 7.93% hydrogen, and10.54% sulfur. Theory for the dithio-nosalac methyl ester (C₂₆ H₄₂ O₈S₂) requires 57.11% carbon, 7.74% hydrogen and 11.73% sulfur.

Example 30 (THIO-BIS-DIBSALAC ESTER)

A tenth mole of mono-methyl diisobutenylsuccinate was dissolved in 100ml of xylene and 0.05 mole of SCl₂ was added dropwise to the stirredxylene solution. The mixture was refluxed overnight and rotoevaporatedfor three hours at 90° C. IR analysis revealed that the hemi-ester/SCl₂adduct was completely converted to the desired thio-bis-lactone methylester. A plausible structure for the sulfur-bridged bis-lactone is shownbelow: ##STR20##

Example 31 (THIO-BIS-NOSALAC AMIDE)

A tenth mole (51.3 g) of the adduct of SCl₂ and n-octenyl succinicanhydride described in Example 20 was dissolved in 100 ml chloroform,and 0.2 mole (14.6 g) of diethylamine was added dropwise to thewell-stirred solution at room temperature. The exothermic reactioncaused the reaction temperature to peak to about 50° C., and externalcooling was applied to maintain reaction temperature at about 10° C. Thecooling bath was removed, and the reaction mixture was refluxed for twohours. The evolution of HCl gas occurred. The mixture was rotoevaporatedfor an hour at 80° C. and diluted with 200 ml of ether. Filtrationremoved the Et₂ NH HCl salt that formed. The filtrate was washed withaqueous Na₂ CO₃ (5% soln.) and dried over Na₂ CO₃. Rotoevaporation ofthe ether solution gave a residue which featured an IR spectrum withprominent lactone and amide carbonyl absorption bands at 5.62 and 6.10microns, and analyzed for 63.73% C, 9.36% H, 4.69% N and 5.37% S. Theoryfor the thio-bis-lactone amide (C₃₂ H₅₆ N₂ O₆ S) requires 64.39% C,9.45% H, 4.69% N and 5.37% S.

Example 32

A tenth mole of mono-methyl diisobutenyl succinate was dissolved in 100ml of xylene and a tenth mole (23.5 g) of 2,4-dinitrobenzenesulfenylchloride (dissolved in 100 ml xylene) was added dropwise. The reactionmixture was then refluxed overnight (HCl evolution occurred). Themixture was rotoevaporated using high vacuum at 90° C. for four hours.The residue, featured an IR spectrum with strong lactone and estercarbonyl absorption bands at 5.63 and 5.73 microns.

Example 33 (DIBMALAC ESTER)

0.05 mole (10.4 g) of diisobutenyl maleic anhydride (from diisobutyleneand 2-chloro maleic anhydride) and 0.05 mole (2.4 g) of absolute ethanolwere combined and heated to 95° C. to generate the hemi-ester. At thispoint, a drop of sulfuric acid (95%) was added and the stirred mixtureheated at 100° C. for about an hour. The product (in ether) was washedwith aqueous Na₂ CO₃ (5% solution) and dried over Na₂ CO₃. Vacuumdistillation of the crude product afforded 7.0 g of distillate, b.p118°-119° C. (0.15 mm) which featured an IR spectrum with intenselactone and ester carbonyl absorption bands at 5.63 and 5.7 microns. Thedistilled product analyzed for 66.07% carbon and 8.73% hydrogen. Theoryfor the dibma lactone ester (C₁₄ H₂₂ O₄) requires 66.11% carbon and8.72% hydrogen.

LACTONE OXAZOLINES Example 34--(DIBSALAC OXAZOLINE)

Eleven grams (0.045 mole) of DIBSALAC described in Example 1 weredissolved in 20 ml of xylene and 4.65 g (0.048 mole) of2-amino-2-methyl-1-propanol was added dropwise. The reaction mixture washeated to reflux in a flask equipped with a Dean-Stark moisture trap.After 16 hours, 1.5 ml of water were collected and the xylene wasremoved by rotoevaporation. Vacuum distillation of the residue affordeda colorless liquid, b.p. 135° C. (0.3 mm) in about 85% yield. The liquidgradually crystallized on standing. The crystalline product featured aninfrared spectrum with prominent lactone and oxazoline absorption bandsat about 5.68 and 6.02 microns, and analyzed for 68.15% carbon, 9.48%hydrogen, 4.93% nitrogen and 16.54% oxygen. Theory for the lactoneoxazoline (C₁₆ H₂₇ NO₃) requires 68.28% carbon, 9.6% hydrogen, 4.99%nitrogen and 17.06% oxygen. The proposed structure is shown below.##STR21##

Example 35--(DIBSALAC OXAZOLINE)

DIBSALAC (0.05 mole, 11.4 g) described in Example 1 and 0.05 mole (6.2g) of tris-(hydroxymethyl)-aminomethane (THAM) were added to 25 ml ofxylene in a reactor equipped with a Dean-Stark moisture trap. Themixture was refluxed until ca. 1.6 ml of water were collected in themoisture trap (approximately 5 hours). Infrared analysis indicatedcomplete conversion to lactone oxazoline product. Upon cooling to roomtemperature, the clear solution became cloudy and while solids separatedfrom solution. The solid product was filtered off, washed several timeswith ether, and dried. The first crop weighed 6.0 grams and melted at82°-88° C. Recrystallization from xylene gave a white solid which meltedat 97°-103° C., and featured an IR spectrum with prominent lactonecarbonyl and oxazoline (C═N) absorption bands at 5.66 and 6.0 microns.The recrystallized solid analyzed for 59.87% C, 8.46% H and 4.26% N.Theory for the lactone oxazoline hemi-hydrate (C₁₆ H₂₄ NO₅.1/2H₂ O)requires 60.15% C, 7.89% N, and 4.38% N. The product can be representedby the following structure: ##STR22##

Example 36--(NOSALAC OXAZOLINE)

Nosalac amide (0.025 mole, 5.67 g) described in Example 10 and 0.025mole (3.0 g) of THAM were added to 10 ml of xylene and the mixture wasrefluxed overnight. The solvent was stripped off and the mixture washeated to 200° for two hours, then cooled and dissolved in benzene. Theaddition of ether to the benzene solution caused the gradualprecipitation of solid from solution. The IR spectrum of the solid, m.p.108°-109° C., featured characteristic lactone carbonyl and oxazoline(C═N) absorption bands at 5.63 and 6.0 microns, and analyzed for 61.57%C, 8.38% H and 4.69% N. Theory for the adduct (C₁₆ H₂₇ O₅ N) requires61.32% C, 8.69% H and 4.47% N.

Example 37--(OSALAC OXAZOLINE)

Two-tenths mole (73.6 g) of OSALAC described in Example 4 and 0.2 mole(24.2 g) of tris-hydroxymethyl aminomethane (THAM) were added to 100 mlof xylene contained in a reactor equipped with a Dean-Stark moisturetrap. The mixture was refluxed until 5 ml of water were collected (aboutthree hours) and the xylene solvent was then removed by rotoevaporation.The product was diluted in ether and two crops amounting to 71 g wereisolated by filtration. The product melted at 121°-122° C. and featuredan IR spectrum with prominent lactone carbonyl and oxazoline (C═N)absorption bands. Elemental analyses showed 66.86% C, 10.61% H, 3.45% Nand 12.01% O. Theory for the osalac oxazoline (C₂₆ H₄₇ NO₅) requires66.86% C, 10.44% H, 3.09% N and 12.63% O.

Example 38--(PIBSALAC OXAZOLINE)

Sixty grams (ca. 0.05 mole) of PIBSALAC described in Example 5 and 6.1 g(0.05 mole) of tris-(hydroxymethyl) aminomethane (THAM) were added to 50ml of tetrahydrofuran (THF). The stirred mixture was gradually heated todissolve the reactants.

The THF solvent was then boiled off, and the reaction temperature wasraised to 170° and kept there for about an hour. The residue wasdissolved in hexane filtered and rotoevaporated at 90° C. for fourhours, and diluted with an equal weight of neutral oil. The infraredspectrum of the product featured prominent lactone carbonyl andoxazoline (C═N) absorption bands at 5.63 and 6.0 microns.

The diluted product (50% a.i.) showed a hydroxyl number of 43.1 andanalyzed for 0.69% nitrogen (by Kjeldahl). The basic nitrogen content,determined by non-aqueous titration with perchloric acid was 0.56%.

Example 39--(PIBSALAC OXAZOLINE)

The PIBSALAC prepared in Example 7 and 0.1 mole (12.1 g) oftris-(hydroxylmethyl) aminomethane (THAM) were combined and heated at180° C. for about four hours. The product was diluted in 200 ml hexane,filtered and rotoevaporated at 90° C. for four hours. The residue wasdiluted in an equal weight of neutral oil (S-150N). IR analysis of theproduct showed strong absorption bands at 5.65 and 6.0 micronsascribable to lactone and oxazoline functionality. Analyses revealedthat the polyisobutyl lactone oxazoline product contained 0.63% nitrogenby Kjeldahl's method and 0.56% basic nitrogen as determined bynon-aqueous titration with perchloric acid. The hydroxyl number of thediluted product (50% a.i.) as determined according to AM-S 240.10-1 was51.2.

EXAMPLE 40--(HYDROXY-DIBSALAC OXAZOLINE)

Epoxy pibsa (0.01 mole, 2.26 g) described in Example 11 and THAM (0.01,1.21 g) was dissolved in 10 ml of xylene and refluxed overnight. Removalof the xylene solvent by rotoevaporation gave a concentrate whichfeatured an IR spectrum with the characteristic lactone carbonyl andoxazoline (C═N) absorption bands at 5.70 and 6.01 microns.

EXAMPLE 41--(HYDROXY-PIBSALAC OXAZOLINE)

The hydroxy pibsa lactone acid (ca. 0.05 mole, 130 g of 50% a.i.)described in Example 15 and 0.05 mole (6.05 g) of THAM were mixed andheated to 180° C. for about four hours. The product was diluted in 100ml hexane, filtered and concentrated by rotoevaporation. The dilutedproduct (50% a.i.) featured an IR spectrum with lactone carbonyl andoxazoline (C═N) absorption bands at 5.7 and 6.03 microns and analyzedfor 0.57% nitrogen (Kjeldahl).

EXAMPLE 42--(THIO-BIS-OSALAC OXAZOLINE)

Thio-bis:osalac (0.05 mole, 38.4 g) described in Example 23 and THAM(0.1 mole, 12.1 g) were added to xylene (200 ml) in a reactor fittedwith a moisture trap. The mixture was refluxed until about 3 ml of waterwere collected in the moisture trap (three hours). The hazy xylenesolution was filtered, and diluted with acetone to the cloud point. Thesolids that separated from solution were recovered by filtration. Fourcrops amounting to 47.5 g were collected. The solid product, m.p.171°-175° C. featured an IR spectrum with prominent absorption bands at5.63 and 6.0 microns, and analyzed for 64.95% C, 9.07% H, 3.03% N and2.92% S. Theory for the thio-bis-lactone oxazoline (C₅₂ H₉₂ N₂ O₁₀ S)requires 66.63% C, 9.89% H, 3.00% N and 3.42% S. A plausible structureis shown below: ##STR23##

EXAMPLE 43--(THIO-BIS-PIBSALAC OXAZOLINE)

Thio-bis-pibsalac (0.01 mole, 26.3 g) described in Example 26, THAM(0.02 mole, 2.42), and 0.01 g of zinc acetate were added to 26 g ofneutral oil (S-150N) and heated to 180° C. for about two hours. The IRspectrum of the product showed absorption bands at 5.65 (lactone) and6.0 (oxazoline) microns. The diluted product (50% a.i.) analyzed for0.54% N.

EXAMPLE 44--Chemical Stability of PIBSALAC OXAZOLINE

Fifteen grams of the product of Example 38 and 1 gram of THAM werecombined and heated at 195° C. for six hours. The infrared spectrum ofthe reaction mixture was virtually identical to that of the PIBSALACOXAZOLINE reactant indicating that the lactone oxazoline was resistantto further aminolysis by THAM. By way of contrast, treatment ofpolybutenyl succinic anhydride/mono-THAM ester (formed by reactingpolybutenyl succinic anhydride with one mole of THAM at 170° for severalhours) with THAM under similar conditions converted the mono-oxazolineester completely to the bis-oxazoline product in less than an hour.

EXAMPLE 45--Thermal Stability of PIBSALAC OXAZOLINE

Heating the product of Example 38 at 200° C. for about 20 hours causedno observable changes in its infrared spectrum. Under similarthermolysis conditions, polybutenyl-bis-oxazoline (prepared frompolybutenyl succinic anhydride and 2 moles of THAM at 180° for 2 hours)showed distinct changes in its infrared spectrum. Heating caused thedominant absorption band at 6.0 microns (C═N stretching) (characteristicof oxazolines) to gradually diminish and become less intense than theimidetype absorption band (at about 5.85 microns) which eventuallydominated the spectrum of the thermalized material after 20 hours.

EXAMPLE 46--Sludge Inhibition Bench (SIB) Test

The product of Example 38 and two other dispersant additives weresubjected to a Sludge Inhibition Bench (SIB) Test which has been foundafter a large number of evaluations, to be an excellent test forassessing the dispersing power of lubricating oil dispersant additives.

The medium chosen for the Sludge Inhibition Bench Test was a usedcrankcase mineral lubricating oil composition having an originalviscosity of about 325 SUS at 100° F. that had been used in a taxicabthat was driven generally for short trips only, thereby causing abuildup of a high concentration of sludge precursors. The oil that wasused contained only a refined base mineral lubricating oil, a viscosityindex improver, a pour point depressant and zinc dialkyldithiophosphateantiwear additive. The oil contained no sludge dispersants. A quantityof such used oil was acquired by draining and refilling the taxicabcrankcase at 1000-2000 mile intervals.

The Sludge Inhibition Bench Test is conducted in the following manner.The aforesaid used crankcase oil, which is milky brown in color, isfreed of sludge by centifuging for ×1/2 hour at about 39,000 gravities(gs.). The resulting clear bright red supernatant oil is then decantedfrom the insoluble sludge particles thereby separated out. However, thesupernatant oil still contains oil-soluble sludge precursors which onheating under the conditions employed by this test will tend to formadditional oil-insoluble deposits of sludge. The sludge inhibitingproperties of the additives being tested are determined by adding toportions of the supernatant used oil, a small amount, such as 0.5, 1.0or 1.5 weight percent, on an active ingredient basis, of the particularadditive being tested. Ten grams of each blend being tested is placed ina stainless steel centrifuge tube and is heated at 280° F. for 16 hoursin the presence of air. Following the heating, the tube containing theoil being tested is cooled and then centrifuged for 30 minutes at about39,000 gs. Any deposits of new sludge that form in this step areseparated from the oil by decanting the supernatant oil and thencarefully washing the sludge deposits with 15 ml. of pentane to removeall remaining oil from the sludge. Then the weight of the new solidsludge that has been formed in the test, in milligrams, is determined bydrying the residue and weighing it. The results, are reported asmilligrams of sludge per 10 grams of oil, thus measuring differences assmall as 1 part per 10,000. The less new sludge formed the moreeffective is the additive as a sludge dispersant. In other words, if theadditive is effective, it will hold at least a portion of the new sludgethat forms on heating and oxidation, stably suspended in the oil so itdoes not precipitate down during the centrifuging.

Using the above describe test, the dispersant action of thelactone-oxazoline additives of the present invention was compared withthe dispersing power of a commercial dispersant referred to asPIBSA/TEPA. The PIBSA/TEPA was prepared by reaction of 1 mole oftetraethylene pentamine with 1.5 moles of polyisobutenyl succinicanhydride (Sap. No. 80) obtained from polyisobutylene of about 1000number average molecular weight. The PIBSA/TEPA dispersant was used inthe form of an additive concentrate containing about 50 weight percentPIBSA/TEPA in 50 wt. % mineral lubricating oil. This PIBSA/TEPA additiveconcentrate analyzed about 1.8% nitrogen, indicating that the activeingredient, i.e., PIBSA/TEPA per se, contained about 3.6% nitrogen.

In addition, the lactone-oxazoline product of the present invention wasalso compared with polyisobutenylsuccinic anhydride-bis oxazolinematerial prepared in accordance with the teachings of DOS 2512201 in theSludge Inhibition Bench Test. The bis-oxazoline designated PIBSA/BisTHAM dispersant was prepared via the reaction of 2 molar proportions oftris-(hydroxymethyl) aminomethane with polyisobutenylsuccinic anhydrideaccording to the procedure, stoichiometry and reaction conditionsspecified in this patent application. The test results are given in thetable below.

                  TABLE I                                                         ______________________________________                                        SLUDGE DISPERSANCY TEST RESULTS                                                           Mg Sludge/10 g. Oil at                                            Additive      %N     0.5 wt.% 1.00 wt. %                                                                            1.5 wt.%                                ______________________________________                                        of Example 38 0.69   7.70     4.37    0.0                                     Blank                10.0     10.0    10.0                                    PIBSA/BisTHAM 1.0    7.61     4.17    0.56                                    PIBSA/TEPA    1.2    7.78     3.44    2.22                                    ______________________________________                                    

The data of Table I illustrates the outstanding dispersant activity ofthe additive products of the invention when compared a known commercialdispersant referred to as PIBSA-TEPA.

The numerous examples cited above illustrate the novel compositions ofthe invention and the new processes devised in preparing thesecompositions; moreover, the examples further illustrate the superbdispersant properties of the polyisobutyl lactone oxazolines and theirresistance to oxidation and thermolysis provides a means toexceptionally control lubricant viscosity (manifested by decreased oilthickening) in long drain applications.

The oxidation resistance is illustrated by a test in which air isbubbled through lubricant samples maintained at about 160° C. over a48-hour period. Each 300 gram sample is modified by the addition ofabout 5.5 volume percent (50% a.i.) dispersant to measure its respectiveeffect in reducing thickening. 20 parts per million of ironacetylacetonate is added to each sample at the beginning and again atthe end of 24 hours. At the end of the test the results were as follows:

    ______________________________________                                        Example Dispersant Added                                                                             Viscosity Poises @-18° C.                       ______________________________________                                        1       none           46                                                     2       Example 38 additive                                                                          68                                                     3       PIBSA-TEPA     80                                                     ______________________________________                                    

The preparation of the heterosubstituted hydrocarbyl lactone acidmaterials are produced as noted earlier by reaction with afunctionalizing agent of the class consisting of an oxidizing agent or athiylating agent at a temperature of from -20° C. to b 100° C. untilfunctionalization is complete. The preferred oxidizing agent is of theclass consisting of peracids, alkyl hydroperoxides and hydrogen peroxideand preferably used when the temperature is from -20° C. to 50° C. Thepreferred thiylating agents consist of hydrocarbyl sulfenyl halides, asulfur chloride of the formula S_(x) Cl₂ wherein x is an integer of from1 to 4 and chlorosulfonic acid. The thiylating agents are usefullyreacted over the entire range of -20° C. to 100° C. though preferably atfrom about 20° C. to 80° C.

EXAMPLE 47--SULFO PIBSALAC OXAZOLINE

Seventy grams (0.05 mole) of pibsa (MW) 960 with a Sap. No. of about 83)were dissolved in 100 ml of tetrahydrofuran (THF) and 6 g. (0.05 g) ofchlorosulfonic acid were added dropwise to the stirred THF solution atabout 25° C. The addition was exothermic and external cooling wasnecessary to maintain the reaction temperature at about 25° C. Afteraddition the reaction mixture was stirred at room temperature for anhour, and then 1.0 g of water was added and the mixture was heated atreflux for 2 hours. The THF was stripped off and the residue dissolvedin 200 ml. of hexane. The hexane solution was washed twice with 100 ml.of water, dried, and rotoevaporated at 80° C. for 4 hours. Theconcentrate featured an IR spectrum with strong lactone absorption bandsat 5.6-5.71 microns indicating a mixture of 5- and 6-ring lactones, andanalyzed for 1.92% sulfur.

Twenty-six grams of the sulfo pibsalac were dissolved in 26 g. ofneutral oil, and combined with 5 grams of THAM, and 0.01 g. of ZnAc₂.The mixture was heated to 180° C. for about 4 hours, diluted in hexane,filtered and rotoevaporated at 80° C. for 2 hours. Infrared analysis ofthe product showed the presence of lactone and oxazoline functionality.

The invention in its broader aspects is not limited to the specificdetails shown and described and departures may be made from such detailswithout departing from the principles of the invention and withsacrificing its chief advantages.

What is claimed is:
 1. Oil soluble thio-bis-(hydrocarbyl lactoneoxazoline) useful as an additive in oleaginous compositions; derivedfrom alkenyl succinic anhydride, acid or ester; and represented by theformula: ##STR24## wherein R is selected from the group consisting ofhydrogen and alkyl of 1 to 400 carbon atoms; X is selected from thegroup consisting of C₁ to C₃ alkyl and hydroxy-alkyl of the structure--(CH₂)_(n) OH wherein n is 1 to 3, at least one of said X being hydroxyalkyl; S represents sulfur and z is an integer ranging from 1 to
 4. 2.Lactone oxazoline according to claim 1, wherein each X is a hydroxyalkyl group of the structure --(CH₂)_(n) OH wherein n is 1 to
 3. 3. Athio-bis-(hydrocarbyl lactone oxazoline) according to claim 1, wherein Xis hydroxy alkyl and z is one, said compound being formed by thereaction of polyisobutenylsuccinic acid, having a number averagemolecular weight of about 960, reacted with SCl₂, followed by reactionwith tris-(hydroxymethyl) aminomethane.
 4. An oil solublethio-bis-(hydrocarbyl lactone oxazoline) of claim 1, formed by reactingsaid alkenyl succinic acid with a sulfur chloride and then reacting withan amino alcohol having 4 to 8 carbon atoms of the formula: ##STR25##where X is selected from the group consisting of alkyl and hydroxyalkyl.
 5. A compound according to claim 4, wherein said amino alcohol istris-(hydroxymethyl) aminomethane.
 6. A compound according to claim 4,wherein said alkenyl succinic acid is polyisobutenyl succinic acid, saidpolyisobutenyl group having a molecular weight in the range of about 900to
 3000. 7. A thio-bis-(hydrocarbyl lactone oxazoline) according toclaim 1, formed by the reaction of polyisobutenylsuccinic acid, saidpolyisobutenyl group having a molecular weight in the range of about 900to 3000, with sulfur halide, followed by reaction withtris-(hydroxymethyl) aminomethane.